Primary intermediates for oxidative coloration of hair

ABSTRACT

Primary intermediates for hair coloring compositions for oxidative dyeing of hair are compounds of the formula (1):  
                 
 
     wherein R is hydrogen, hydroxy, nitro, amino, halogen, C 1  to C 5  alkyl or haloalkyl, C 1  to C 5  alkoxy or cyclic alkoxy, C 1  to C 5  hydroxyalkyl and C 1  to C 5  hydroxyalkoxy; Ar is an aromatic group, preferably an aromatic group selected from a furanyl, thienyl, pyridinyl, phenyl, 2,3-dihydro-benzo[1,4]dioxin-5 or -6-yl or benzo[1,3]dioxol-4 or -5-yl group; and y=1 to 3.

FIELD OF THE INVENTION

[0001] This invention relates to new 4-amino-2-(1-aryloxy-ethyl)phenolcompounds and compositions containing these compounds as primaryintermediates for oxidative coloring of hair fibers.

BACKGROUND TO THE INVENTION

[0002] Coloration of hair is a procedure practiced from antiquityemploying a variety of means. In modern times, the method mostextensively to color hair is an oxidative dyeing process utilizing oneor more oxidative hair coloring agents in combination with one or moreoxidizing agents.

[0003] Most commonly a peroxy oxidizing agent is used in combinationwith one or more oxidative hair coloring agents, generally smallmolecules capable of diffusing into hair and comprising one or moreprimary intermediates and one or more couplers. In this procedure, aperoxide material, such as hydrogen peroxide, is employed to activatethe small molecules of primary intermediates so that they react withcouplers to form larger sized compounds in the hair shaft to color thehair in a variety of shades and colors.

[0004] A wide variety of primary intermediates and couplers have beenemployed in such oxidative hair coloring systems and compositions. Amongthe primary intermediates employed there may be mentionedp-phenylenediamine, p-toluenediamine, p-aminophenol,4-amino-3-methylphenol, N,N-bis(2-hydroxyethyl)-p- phenylene diamine,1-(2-hydroxyethyl)-4,5-diaminopyrazole and as couplers there may bementioned resorcinol, 2-methylresorcinol, 3-aminophenol,2,4-diaminophenoxyethanol, and 5-amino-2-methylphenol.

[0005] There are numerous additional requirements for oxidation dyecompounds that are used to dye human hair besides the color or thedesired intensity. Thus, the dye compounds must be unobjectionable inregard to toxicological and dermatological properties and must providethe desired hair color with a good light fastness, fastness to apermanent wave treatment, acid fastness and fastness to rubbing. Thecolor of the hair dyed with the dye compounds in each case must bestable for at least 4 to 6 weeks to light, rubbing and chemical agents.Furthermore, an additional requirement is the production of a broadpalette of different color shades using different developer and couplersubstances. Many of the desired shades have been produced with dyesbased on p-aminophenol. However, as indicated in U.S. Pat. No.4,997,451, the use of p-aminophenol is being questioned for possibletoxicological reasons. The proposed replacements for p-aminophenol havenot proved entirely satisfactory. There is therefore a need for newprimary intermediate compounds to meet one or more of the desiredproperties but not possessing the possible toxicological drawbackspossessed by p-aminophenol.

SUMMARY OF THE INVENTION

[0006] It is therefore an object of this invention to provide newprimary intermediate compounds useful in place of p-aminophenol toprovide a wide range of different color shades with various combinationsof primary intermediates and couplers, but which do not have thetoxicological drawbacks possessed by p-aminophenol.

[0007] It has been discovered that new 4-amino-2-(1-aryloxy-ethyl)phenolcompounds are suitable primary intermediates for hair coloringcompositions and systems for providing good oxidative coloration of hairand for providing acceptable light fastness, good selectivity, fastnessto shampooing, fastness to perspiration and permanent wave treatment,and suitable for providing a wide variety of different color shades withvarious primary intermediate and coupler compounds.

[0008] The invention provides new 4-amino-2-(1-aryloxy-ethyl)phenolcompounds of Formula (1):

[0009] wherein R is hydrogen, hydroxy, nitro, amino, halogen, C₁ to C₅alkyl or haloalkyl, C₁ to C₅ alkoxy or cyclic alkoxy, C₁ to C₅hydroxyalkyl and C₁ to C₅ hydroxyalkoxy; Ar is an aromatic group,preferably an aromatic group selected from a furanyl, 2- or 3-thienyl,pyridinyl, phenyl, 2,3-dihydro-benzo[1,4]dioxin-5 or -6-yl orbenzo[1,3]dioxol-4 or -5-yl group; and y =1 to 3. The halogen may befluorine, chlorine, bromine or iodine, preferable fluorine or chlorine.

[0010] These novel primary intermediates are used to provide colorationto hair in which there is good dye uptake by the hair and providesshades or colors which are stable over a relatively long period of time.The novel primary intermediates provide for dyeing of hair to impartcolor or shades that possess good wash fastness and do not undergosignificant changes on exposure to light or shampooing.

DETAILED DESCRIPTION OF THE INVENTION

[0011] Preferred 4-amino-2-(1-aryloxy-ethyl)phenol compounds of thisinvention are those of formula (1)

[0012] wherein R is hydrogen, amino or C₁ to C₃ alkyl, and Ar is phenyl,pyridinyl, furanyl, 2- or 3-thienyl, 2,3-dihydro-benzo[1,4]dioxin-5 or-6-yl or benzo[1,3]dioxol-4 or -5-yl.

[0013] The compounds of formula (1) can be prepared by the followingreaction procedure where R, Ar and y are as defined hereinbefore:

[0014] In this synthesis the new 4-amino-2-(1-aryloxy-ethyl)-phenolcompounds of formula (1) of this invention can be prepared by thehydrolysis of 5-butylamido-2-hydroxyacetophenone of formula (2) withmethanolic HCl to produce a compound of formula (3), then protecting thehydroxyl and amino groups of the formula (3) compound by treatmentthereof with di-tert-butyl dicarbonate [(Boc)₂O] to give a compound offormula (4) followed by reduction of the formula (4) compound with areducing agent such as sodium borohydride (NaBH₄) to produce a compoundof formula (5) which is subjected to the Mitsunobu reaction with areagent of the formula HO—Ar—(R)_(y) in the presence of triphenylphosphine and diethyl azodicarboxylate or diisopropyl azodicarboxylateto produce a compound of formula (6), which is deprotected withmethanolic HCl to produce a compound of formula (1).

SYNTHESIS EXAMPLES 1 TO 11

[0015] Employing the appropriate reagent of the formula HO—Ar—(R)_(y) inthe this reaction procedure the following compounds of formula (1) canbe prepared:

[0016] 4-amino-2-(1-phenoxy-ethyl)-phenol

[0017] 4-amino2-[1-(4-amino-3-methyl-phenoxy)-ethyl]-phenol;

[0018] 4-amino-2-[1-(pyridin-3-yloxy)-ethyl]-phenol;

[0019] 4-amino-2-[1-thien-2-yloxy)-ethyl]-phenol;

[0020] 4-amino-2-[1-(furan-2-yloxy)-ethyl]-phenol;

[0021] 4-amino-2-[1-(4-amino-phenoxy)-ethyl]-phenol;

[0022]4-amino-2-{1-(2,3-dihydro-benzo[1,4]dioxin-6-yloxy)-ethyl}-phenol;

[0023] 4-amino-2-[1-(5-bromo-furan-2-yloxy)-ethyl)-phenol;

[0024] 4-amino-2-[1-(4-chloromethyl-phenoxy)-ethyl]-phenol;

[0025] 4-amino-2-[1-(4-methoxy-phenoxy)-ethyl]-phenol; and

[0026] 4-amino-2-{1-(benzo[1,3]dioxin-5-yloxy)-ethyl}-phenol.

[0027] As used herein, the term “hair dyeing composition” (alsosynonymously referred to herein as the hair dye composition, the haircoloring composition, or the hair dye lotion) refers to the compositioncontaining oxidation dyes, including the novel compounds describedherein, prior to admixture with the developer composition. The term“developer composition” (also referred to as the oxidizing agentcomposition or the peroxide composition) refers to compositionscontaining an oxidizing agent prior to admixture with the hair dyeingcomposition. The term “hair dye product” or “hair dye system” (alsoreferred to as the hair dyeing system, hair dyeing product, or haircoloring system) interchangeably refer to the combination of the hairdyeing composition and the developer composition before admixture, andmay further include a conditioner product and instructions, such productor system often being provided packaged as a kit. The term “hair dyeingproduct composition” refers to the composition formed by mixing the hairdyeing composition and the developer composition. “Carrier” (or vehicleor base) refers to the combination of ingredients contained in acomposition excluding the active agents (e.g., the oxidation hair dyesof the hair dyeing composition).

[0028] Hair coloring (i.e., hair dyeing) compositions of this inventioncan contain, in combination with oxidation dye couplers, a novel primaryintermediate of this invention as the sole primary intermediate or canalso contain other primary intermediates. Thus, one or more suitableprimary intermediates may be used in combination with the novel primaryintermediates of this invention.

[0029] Suitable known primary intermediates include, for example,

[0030] p-phenylenediamine derivatives such as: benzene-1,4-diamine(commonly known as p-phenylenediamine), 2-methyl-benzene-1,4-diamine,2-chloro-benzene-1,4-diamine, N-phenyl-benzene-1,4-diamine,N-(2-ethoxyethyl)benzene-1,4-diamine,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, (commonly known asN,N-bis(2-hydroxyethyl)-p-phenylenediamine)(2,5-diamino-phenyl)-methanol, 1-(2,5-diamino-phenyl)-ethanol,2-(2,5-diamino-phenyl)-ethanol, N-(4-aminophenyl)benzene-1,4-diamine,2,6-dimethyl-benzene-1,4-diamine, 2-isopropyl-benzene-1,4-diamine,1-[(4-aminophenyl)amino]-propan-2-ol, 2-propyl-benzene-1,4-diamine,1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]propan-2-ol,N⁴,N⁴,2-trimethylbenzene-1,4-diamine, 2-methoxy-benzene-1,4-diamine,1-(2,5-diaminophenyl)ethane-1,2-diol, 2,3-dimethyl-benzene-1,4-diamine,N-(4-amino-3-hydroxy-phenyl)-acetamide, 2,6-diethylbenzene-1,4-diamine,2,5-dimethylbenzene-1,4-diamine, 2-thien-2-ylbenzene-1,4-diamine,2-thien-3-ylbenzene-1,4-diamine, 2-pyridin-3-ylbenzene-1,4-diamine,1,1′-biphenyl-2,5-diamine, 2-(methoxymethyl)benzene-1,4-diamine,2-(aminomethyl)benzene-1,4-diamine, 2-(2,5-diaminophenoxy)ethanol,N-[2-(2,5-diaminophenoxy)ethyl]-acetamide,N,N-dimethylbenzene-1,4-diamine, N,N-diethylbenzene-1,4-diamine,N,N-dipropylbenzene-1,4-diamine, 2-[(4-aminophenyl)(ethyl)amino]ethanol,2-[(4-amino-3-methyl-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,N-(2-methoxyethyl)-benzene-1,4-diamine,3-[(4-aminophenyl)amino]propan-1-ol,3-[(4-aminophenyl)-amino]propane-1,2-diol,N-{4-[(4-aminophenyl)amino]butyl}benzene-1,4-diamine, and2-[2-(2-{2-[(2,5-diaminophenyl)-oxy]ethoxy}ethoxy)ethoxy]benzene-1,4-diamine;

[0031] p-aminophenol derivatives such as: 4-amino-phenol (commonly knownas p-aminophenol), 4-methylamino-phenol, 4-amino-3-methyl-phenol,4-amino-2-hydroxymethyl-phenol, 4-amino-2-methyl-phenol,4-amino-2-[(2-hydroxy-ethylamino)-methyl]-phenol,4-amino-2-methoxymethyl-phenol, 5-amino-2-hydroxy-benzoic acid,1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol,4-amino-2-(2-hydroxy-ethyl)-phenol, 4-amino-3-(hydroxymethyl)phenol,4-amino-3-fluoro-phenol, 4-amino-2-(aminomethyl)-phenol, and4-amino-2-fluoro-phenol;

[0032] o-aminophenol derivatives such as: 2-amino-phenol (commonly knownas o-aminophenol), 2,4-diaminophenol, 2-amino-5-methyl-phenol,2-amino-6-methyl-phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide, and2-amino-4-methyl-phenol; and

[0033] heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine(commonly known as 2,4,5,6-tetraaminopyridine),1-methyl-1H-pyrazole-4,5-diamine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,N²,N²-dimethyl-pyridine-2,5-diamine, 2-[(3-amino-6-methoxypyridin-2-yl)amino]ethanol, 6-methoxy-N²-methyl-pyridine-2,3-diamine,2,5,6-triaminopyrimidin-4(1H)-one, pyridine-2,5-diamine,1-isopropyl-1H-pyrazole-4,5-diamine,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine,1-(benzyl)-1H-pyrazole-4,5-diamine, and1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine.

[0034] The novel primary intermediates of formula (1) of this inventionmay be used with any suitable coupler(s) in hair coloring compositionsor systems of this invention.

[0035] Suitable known couplers include, for example:

[0036] phenols, resorcinol and naphthol derivatives such as:naphthalene-1,7-diol, benzene-1,3-diol, 4-chlorobenzene-1,3-diol,naphthalen-1-ol, 2-methyl-naphthalen-1-ol, naphthalene-1,5-diol,naphthalene-2,7-diol, benzene-1,4-diol, 2-methyl-benzene-1,3-diol,7-amino-4-hydroxy-naphthalene-2-sulfonic acid,2-isopropyl-5-methylphenol, 1,2,3,4-tetrahydro-naphthalene-1,5-diol,2-chloro-benzene-1,3-diol, 4-hydroxy-naphthalene-1-sulfonic acid,benzene-1,2,3-triol, naphthalene-2,3-diol,5-dichloro-2-methylbenzene-1,3-diol, 4,6-dichlorobenzene-1,3-diol, and2,3-dihydroxy-[1,4]naphthoquinone;

[0037] m-phenylenediamines such as: 2,4-diaminophenol,benzene-1,3-diamine, 2-(2,4-diamino-phenoxy)-ethanol,2-[(3-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,2-mehyl-benzene-1,3-diamine,2-[[2-(2,4-diamino-phenoxy)-ethyl]-(2-hydroxy-ethyl)-amino]-ethanol,4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine,2-(2,4-diamino-phenyl)-ethanol,2-(3-amino-4-methoxy-phenylamino)-ethanol,4-(2-amino-ethoxy)-benzene-1,3-diamine, (2,4-diamino-phenoxy)-aceticacid, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol,4-ethoxy-6-methyl-benzene-1,3-diamine,2-(2,4-diamino-5-methyl-phenoxy)-ethanol,4,6-dimethoxy-benzene-1,3-diamine,2-[3-(2-hydroxy-ethylamino)-2-methyl-phenylamino]-ethanol,3-(2,4-diamino-phenoxy)-propan-1-ol, N-[3-(dimethylamino)phenyl]urea,4-methoxy-6-methylbenzene-1,3-diamine,4-fluoro-6-methylbenzene-1,3-diamine,2-({3-[(2-hydroxyethyl)amino]-4,6-dimethoxyphenyl}-amino)ethanol,3-(2,4-diaminophenoxy)-propane-1,2-diol,2-[2-amino-4-(methylamino)-phenoxy]ethanol,2-[(5-amino-2-ethoxy-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,2-[(3-aminophenyl)amino]ethanol, N-(2-aminoethyl)benzene-1,3-diamine,4-{[(2,4-diamino-phenyl)oxy]methoxy}-benzene-1,3-diamine, and2,4-dimethoxybenzene-1,3-diamine;

[0038] m-aminophenols such as: 3-amino-phenol,2-(3-hydroxy-4-methyl-phenylamino)-acetamide,2-(3-hydroxy-phenylamino)-acetamide, 5-amino-2-methyl-phenol,5-(2-hydroxy-ethylamino)-2-methyl-phenol, 5-amino-2,4-dichloro-phenol,3-amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol,5-amino-2-(2-hydroxy-ethoxy)-phenol,2-chloro-5-(2,2,2-trifluoro-ethylamino)-phenol,5-amino-4-chloro-2-methyl-phenol, 3-cyclopentylamino-phenol,5-[(2-hydroxyethyl)amino]-4-methoxy-2-methyl phenol,5-amino-4-methoxy-2-methylphenol, 3-(dimethylamino)phenol,3-(diethylamino)phenol, 5-amino-4-fluoro-2-methylphenol,5-amino-4-ethoxy-2-methyl phenol, 3-amino-2,4-dichloro-phenol,3-[(2-methoxyethyl)amino]phenol, 3-[(2-hydroxyethyl)amino]phenol,5-amino-2-ethyl-phenol, 5-amino-2-methoxyphenol,5-[(3-hydroxypropyl)amino]-2-methyl phenol,3-[(3-hydroxy-2-methylphenyl)-amino]propane-1,2-diol, and3-[(2-hydroxyethyl)amino]-2-methylphenol; and

[0039] heterocyclic derivatives such as:3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one,6-methoxyquinolin-8-amine, 4-methylpyridine-2,6-diol,2,3-dihydro-1,4-benzodioxin-5-ol, 1,3-benzodioxol-5-ol,2-(1,3-benzodioxol-5-ylamino)ethanol, 3,4-dimethylpyridine-2,6-diol,5-chloropyridine-2,3-diol, 2,6-dimethoxypyridine-3,5-diamine,1,3-benzodioxol-5-amine,2-{[3,5-diamino-6-(2-hydroxy-ethoxy)-pyridin-2-yl]oxy}-ethanol,1H-indol-4-ol, 5-amino-2,6-dimethoxypyridin-3-ol, 1H-indole-5,6-diol,1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol,6-bromo-1,3-benzodioxol-5-ol, 2-aminopyridin-3-ol, pyridine-2,6-diamine,3-[(3,5-diaminopyridin-2-yl)oxy]propane-1,2-diol,5-[(3,5-diaminopyridin-2-yl)oxy]pentane-1,3-diol, 1H-indole-2,3-dione,indoline-5,6-diol, 3,5-dimethoxypyridine-2,6-diamine,6-methoxypyridine-2,3-diamine, and3,4-dihydro-2H-1,4-benzoxazin-6-amine.

[0040] Preferred primary intermediates include:

[0041] p-phenylenediamine derivatives such as:2-methyl-benzene-1,4-diamine, benzene-1,4-diamine,1-(2,5-diamino-phenyl)-ethanol, 2-(2,5-diamino-phenyl)-ethanol,N-(2-methoxyethyl)benzene-1,4-diamine,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, and1-(2,5-diaminophenyl)ethane-1,2-diol;

[0042] p-aminophenol derivatives such as 4-amino-phenol,4-methylamino-phenol, 4-amino-3-methyl-phenol,4-amino-2-methoxymethyl-phenol, and1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol;

[0043] o-aminophenol derivatives such as: 2-amino-phenol,2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol,N-(4-amino-3-hydroxy-phenyl)-acetamide, and 2-amino-4-methyl-phenol; and

[0044] heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine,1-methyl-1H-pyrazole-4,5-diamine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine,1-(benzyl)-1H-pyrazole-4,5-diamine, andN²,N²-dimethyl-pyridine-2,5-diamine.

[0045] Preferred couplers include:

[0046] phenols, resorcinol and naphthol derivatives such as:naphthalene-1,7-diol, benzene-1,3-diol, 4-chlorobenzene-1,3-diol,naphthalen-1-ol, 2-methyl-naphthalen-1-ol, naphthalene-1,5-diol,naphthalene-2,7-diol, benzene-1,4-diol, 2-methyl-benzene-1,3-diol, and2-isopropyl-5-methyl phenol;

[0047] m-phenylenediamines such as: benzene-1,3-diamine,2-(2,4-diamino-phenoxy)-ethanol,4-{3-[(2,4-diaminophenyl)oxy]propoxy}benzene-1,3-diamine,2-(3-amino-4-methoxy-phenylamino)-ethanol,2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and3-(2,4-diamino-phenoxy)-propan-1-ol;

[0048] m-aminophenols such as: 3-amino-phenol, 5-amino-2-methyl-phenol,5-(2-hydroxy-ethylamino)-2-methyl-phenol, and 3-amino-2-methyl-phenol;and

[0049] heterocyclic derivatives such as:3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1,3-benzodioxol-5-ol,1,3-benzodioxol-5-amine, 1H-indol-4-ol, 1H-indole-5,6-diol,1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol, 1H-indole-2,3-dione,pyridine-2,6-diamine, and 2-aminopyridin-3-ol.

[0050] Most preferred primary intermediates include:

[0051] p-phenylenediamine derivatives such as:2-methyl-benzene-1,4-diamine, benzene-1,4-diamine,2-(2,5-diamino-phenyl)-ethanol, 1-(2,5-diamino-phenyl)-ethanol, and2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol;

[0052] p-aminophenol derivatives such as: 4-amino-phenol,4-methylamino-phenol, 4-amino-3-methyl-phenol, and1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol;

[0053] o-aminophenols such as: 2-amino-phenol, 2-amino-5-methyl-phenol,2-amino-6-methyl-phenol, and N-(4-amino-3-hydroxy-phenyl)-acetamide; and

[0054] heterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine, and1-(benzyl)-1H-pyrazole-4,5-diamine.

[0055] Most preferred couplers include:

[0056] phenols, resorcinol and naphthol derivatives such as:benzene-1,3-diol, 4-chlorobenzene-1,3-diol, naphthalen-1-ol,2-methyl-naphthalen-1-ol, and 2-methyl-benzene-1,3-diol;

[0057] m-phenylenediamine such as: 2-(2,4-diamino-phenoxy)-ethanol,2-(3-amino-4-methoxy-phenylamino)-ethanol,2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and3-(2,4-diamino-phenoxy)-propan-1-ol;

[0058] m-aminophenols such as: 3-amino-phenol, 5-amino-2-methyl-phenol,5-(2-hydroxy-ethylamino)-2-methyl-phenol, and 3-amino-2-methyl-phenol;and

[0059] heterocyclic derivatives such as:3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1H-indol-6-ol, and2-aminopyridin-3-ol.

[0060] Understandably, the coupler compounds and the primaryintermediate compounds, including the novel compounds of the invention,in so far as they are bases, can be used as free bases or in the form oftheir physiologically compatible salts with organic or inorganic acids,such as hydrochloric, citric, acetic, tartaric, or sulfuric acids, or,in so far as they have aromatic OH groups, in the form of their saltswith bases, such as alkali phenolates.

[0061] The total amount of dye precursors (e.g., primary intermediateand coupler compounds, including the novel compounds of this invention)in the hair dyeing compositions of this invention is generally fromabout 0.002 to about 20, preferably from about 0.04 to about 10, andmost preferably from about 0.1 to about 7.0 weight percent, based on thetotal weight of the hair dyeing composition. The primary intermediateand coupler compounds are generally used in molar equivalent amounts.However, it is possible to use the primary intermediate compounds ineither excess or deficiency, i.e., a molar ratio of primary intermediateto coupler generally ranging from about 5:1 to about 1:5.

[0062] The hair dyeing compositions of this invention will contain theprimary intermediate of this invention in an effective dyeing amount,generally in an amount of from about 0.001 to about 10 weight percent byweight of the hair dye composition, preferably from about 0.01 to about5.0 weight percent. Other primary intermediates, when present, aretypically present in an amount such that in aggregate the concentrationof primary intermediates in the composition is from about 0.002 to about10 weight percent, preferably from about 0.01 to about 5.0 weightpercent. The coupler(s) are present in an effective dyeingconcentration, generally an amount of from about 0.001 to about 10.0weight percent by weight of the hair dye composition, preferably fromabout 0.01 to about 5.0 weight percent. The remainder of the hair dyecomposition comprises a carrier or vehicle for the couplers and primaryintermediates, and comprises various adjuvants as described below.

[0063] Any suitable carrier or vehicle, generally an aqueous orhydroalcoholic solution, can be employed, preferably an aqueoussolution. The carrier or vehicle will generally comprise more than 80weight percent of the hair dye composition, typically 90 to 99 weightpercent, preferably 94 to 99 weight percent. The hair coloringcompositions of this invention may contain as adjuvants one or morecationic, anionic, amphoteric, or zwitterionic surface active agents,perfumes, antioxidants such as ascorbic acid, thioglycolic acid orsodium sulfite, chelating and sequestering agents such as EDTA,thickening agents, alkalizing or acidifying agents, solvents, diluents,inerts, dispersing agents, penetrating agents, defoamers, enzymes, andother dye agents (e.g., synthetic direct and natural dyes). Theseadjuvants are cosmetic additive ingredients commonly used incompositions for coloring hair.

[0064] The hair dye compositions of the present invention are used byadmixing them with a suitable oxidant, which reacts with the hair dyeprecursors to develop the hair dye. Any suitable oxidizing agent can beemployed in the hair dye product compositions of this invention,particularly hydrogen peroxide (H₂O₂) or precursors therefor. Alsosuitable are urea peroxide, the alkali metal salts of persulfate,perborate, and percarbonate, especially the sodium salt, and melamineperoxide. The oxidant is usually provided in an aqueous compositiongenerally referred to as the developer composition, which normally isprovided as a separate component of the finished hair dye product andpresent in a separate container. The developer composition may alsocontain, to the extent compatible, various ingredients needed to formthe developer composition, i.e., peroxide stabilizers, foam formers,etc., and may incorporate one or more of the adjuvants referred toabove, e.g., surface active agents, thickeners, pH modifiers, etc. Uponmixing the hair coloring composition and the developer composition toform a hair dye product composition, the adjuvants are provided in thehair dye product composition as it is applied to the hair to achievedesired product attributes, e.g., pH, viscosity, rheology, etc.

[0065] The form of the hair dye product compositions according to theinvention can be, for example, a solution, especially an aqueous oraqueous-alcoholic solution. However, the form that is preferred is athick liquid, cream, gel or an emulsion whose composition is a mixtureof the dye ingredients with the conventional cosmetic additiveingredients suitable for the particular preparation.

[0066] Suitable conventional cosmetic additive ingredients useful in thehair dye and developer compositions, and hence in the hair dye productcompositions of this invention are described below, and may be used toobtain desired characteristics of the hair dye, developer and hair dyeproduct compositions.

[0067] Solvents:

[0068] In addition to water, solvents that can be used are loweralkanols (e.g., ethanol, propanol, isopropanol, benzyl alcohol); polyols(e.g., carbitols, propylene glycol, hexylene glycol, glycerin). See WO98/27941 (section on diluents) incorporated by reference. See also US6027538 incorporated by reference. Under suitable processing, higheralcohols, such as C8 to C18 fatty alcohols, especially cetyl alcohol,are suitable organic solvents, provided they are first liquified bymelting, typically at low temperature (50 to 80° C.), beforeincorporation of other, usually lipophilic, materials.

[0069] The organic solvents are typically present in the hair dyecompositions in an amount of from about 5 to about 30% by weight of thehair dye composition. Water is usually present in an amount of fromabout 5 to about 90% by weight of the hair dye composition, preferablyfrom about 15 to about 75% by weight and most preferably from about 30to about 65% by weight.

[0070] Surfactants:

[0071] These materials are from the classes of anionic, cationic,amphoteric (including zwitterionic surfactants) or nonionic surfactantcompounds. (Cationic surfactants, generally included as hairconditioning materials, are considered separately below.) Suitablesurfactants, other than cationic surfactants, include fatty alcoholsulfates, ethoxylated fatty alcohol sulfates, alkylsulfonates,alkylbenzensulfonates, alkyltrimethylammonium salts, alkylbetaines,ethoxylated fatty alcohols, ethoxylated fatty acids, ethoxylatedalkylphenols, block polymers of ethylene and/or propylene glycol,glycerol esters, phosphate esters, fatty acid alkanol amides andethoxylated fatty acid esters, alkyl sulfates, ethoxylated alkylsulfates, alkyl glyceryl ether sulfonates, methyl acyl taurates, acylisethionates, alkyl ethoxy carboxylates, fatty acid mono- anddiethanolamides. Especially useful are sodium and ammonium alkylsulfates, sodium and ammonium ether sulfates having 1 to 3 ethyleneoxide groups, and nonionic surfactants sold as Tergitols, e.g., C11-C15Pareth-9, and Neodols, e.g., C12-C15 Pareth-3. They are included forvarious reasons, e.g., to assist in thickening, for forming emulsions,to help in wetting hair during application of the hair dye productcomposition, etc. Amphoteric surfactants include, for example, theasparagine derivatives as well betaines, sultaines, glycinates andpropionates having an alkyl or alkylamido group of from about 10 toabout 20 carbon atoms. Typical amphoteric surfactants suitable for usein this invention include lauryl betaine, lauroamphoglycinate,lauroamphopropionate, lauryl sultaine, myristamidopropyl betaine,myristyl betaine, stearoamphopropylsulfonate, cocamidoethyl betaine,cocamidopropyl betaine, cocoamphoglycinate, cocoamphocarboxypropionate,cocoamphocarboxyglycinate, cocobetaine, and cocoamphopropionate.Reference is made to WO 98/52523 published Nov. 26, 1998 and WO 01/62221published Aug. 30, 2001, both incorporated herein by reference thereto.

[0072] The amount of surfactants in the hair dye compositions isnormally from about 0.1% to 30% by weight, preferably 1% to 15% byweight.

[0073] Thickeners:

[0074] Suitable thickeners include such as higher fatty alcohols,starches, cellulose derivatives, petrolatum, paraffin oil, fatty acidsand anionic and nonionic polymeric thickeners based on polyacrylic andpolyurethane polymers. Examples are hydroxyethyl cellulose,hydroxymethylcellulose and other cellulose derivatives, hydrophobicallymodified anionic polymers and nonionic polymers, particularly suchpolymers having both hydrophilic and hydrophobic moieties (i.e.,amphiphilic polymers). Useful nonionic polymers include polyurethanederivatives such as PEG-150/stearyl alcohol/SDMI copolymer. Suitablepolyether urethanes are Aculyn® 44 and Aculyn® 46 polymers sold by Rohm& Haas. Other useful amphiphilic polymers are disclosed in U.S. Pat. No.6,010,541 incorporated by reference. See also WO 01/62221 mentionedabove. Examples of anionic polymers that can be used as thickeners areacrylates copolymer, acrylates/ceteth-20 methacrylates copolymer,acrylates/ceteth-20 itaconate copolymer, and acrylates/beheneth-25acrylates copolymers. In the case of the associative type of thickeners,e.g., Aculyns 22, 44 and 46, the polymer may be included in one ofeither the hair dye composition or the developer composition of the hairdye product and the surfactant material in the another. Thus, uponmixing of the hair dye and developer compositions, the requisiteviscosity is obtained. The thickeners are provided in an amount toprovide a suitably thick product as it is applied to the hair. Suchproducts generally have a viscosity of from 1000 to 100000 cps, andoften have a thixotropic rheology.

[0075] pH Modifying Agents:

[0076] Suitable materials that are used to adjust pH of the hair dyecompositions include alkalizers such alkali metal and ammoniumhydroxides and carbonates, especially sodium hydroxide and ammoniumcarbonate, ammonia, organic amines including methylethanolamine,aminomethylpropanol, mono-, di-, and triethanolamine, and acidulentssuch as inorganic and inorganic acids, for example phosphoric acid,acetic acid, ascorbic acid, citric acid or tartaric acid, hydrochloricacid, etc. See U.S. Pat. No. 6,027,538 incorporated by reference.

[0077] Conditioners:

[0078] Suitable materials include silicones and silicone derivatives;hydrocarbon oils; monomeric quaternary compounds, and quaternizedpolymers. Monomeric quaternary compounds are typically cationiccompounds, but may also include betaines and other amphoteric andzwitterionic materials that provide a conditioning effect. Suitablemonomeric quaternary compounds include behentrialkonium chloride,behentrimonium chloride, benzalkonium bromide or chloride, benzyltriethyl ammonium chloride, bis-hydroxyethyl tallowmonium chloride,C12-18 dialkyldimonium chloride, cetalkonium chloride, ceteartrimoniumbromide and chloride, cetrimonium bromide, chloride and methosulfate,cetylpyridonium chloride, cocamidoproypl ethyldimonium ethosulfate,cocamidopropyl ethosulfate, coco-ethyldimonium ethosulfate,cocotrimonium chloride and ethosulfate, dibehenyl dimonium chloride,dicetyldimonium chloride, dicocodimonium chloride, dilauryl dimoniumchloride, disoydimonium chloride, ditallowdimonium chloride,hydrogenated tallow trimonium chloride, hydroxyethyl cetyl dimoniumchloride, myristalkonium chloride, olealkonium chloride, soyethomoniumethosulfate, soytrimonium chloride, stearalkonium chloride, and manyother compounds. See WO 98/27941 incorporated by reference. Quaternizedpolymers are typically cationic polymers, but may also includeamphoteric and zwitterionic polymers. Useful polymers are 5 exemplifiedby polyquaternium-4, polyquaternium-6, polyquaternium-7,polyquaternium-8, polyquaternium-9, polyquaternium-10,polyquaternium-22, polyquaternium-32, polyquaternium-39,polyquaternium-44 and polyquaternium-47. Silicones suitable to conditionhair are dimethicone, amodimethicone, dimethicone copolyol anddimethiconol. See also WO 99/34770 published Jul. 15, 1999, incorporatedby reference, for suitable silicones. Suitable hydrocarbon oils wouldinclude mineral oil.

[0079] Conditioners are usually present in the hair dye composition inan amount of from about 0.01 to about 5% by weight of the composition.

[0080] Direct Dyes:

[0081] The hair dyeing compositions according to the invention can alsocontain compatible direct dyes including Disperse Black 9, HC Yellow 2,HC Yellow 4, HC Yellow 15, 4-nitro-o-phenylenediamine,2-amino-6-chloro-4-nitrophenol, HC Red 3, Disperse Violet 1, HC Blue 2,Disperse Blue 3, and Disperse Blue 377. These direct dyes can becontained in the hair coloring compositions of the invention in anamount of from about 0.05 to 4.0 percent by weight.

[0082] Natural Ingredients:

[0083] For example, proteins and protein derivatives, and plantmaterials such as aloe, chamomile and henna extracts.

[0084] Other adjuvants include polysaccharides, alkylpolyglycosides,buffers, chelating and sequestrant agents, antioxidants, and peroxidestabilizing agents as mentioned in WO 01/62221, etc.

[0085] The adjuvants referred to above but not specifically identifiedthat are suitable are listed in the International Cosmetics IngredientDictionary and Handbook, (Eighth Edition) published by The Cosmetics,Toiletry, and Fragrance Association, incorporated by reference. Inparticular reference is made to Volume 2, Section 3 (Chemical Classes)and Section 4 (Functions) are useful in identifying a specific adjuvantto achieve a particular purpose or multipurpose.

[0086] The above-mentioned conventional cosmetic ingredients are used inamounts suitable for their functional purposes. For example, thesurfactants used as wetting agents, associative agents, and emulsifiersare generally present in concentrations of from about 0.1 to 30 percentby weight, the thickeners are useful in an amount of from about 0.1 to25 percent by weight, and the hair care functional materials aretypically used in concentrations of from about 0.01 to 5.0 percent byweight.

[0087] The hair dyeing product composition as it is applied to the hair,i.e., after mixing the hair dye composition according to the inventionand the developer, can be weakly acidic, neutral or alkaline accordingto their composition. The hair dye compositions can have pH values offrom about 6 to 11.5, preferably from about 6.8 to about 10, andespecially from about 8 to about 10. The pH of the developer compositionis typically acidic, and generally the pH is from about 2.5 to about6.5, usually about 3 to 5. The pH of the hair dye and developercompositions is adjusted using a pH modifier as mentioned above.

[0088] In order to use the hair coloring composition for dyeing hair,the above-described hair coloring compositions according to theinvention are mixed with an oxidizing agent immediately prior to use anda sufficient amount of the mixture is applied to the hair, according tothe hair abundance, generally from about 60 to 200 grams. Some of theadjuvants listed above (e.g., thickeners, conditioners, etc.) can beprovided in the dye composition or the developer, or both, depending onthe nature of the ingredients, possible interactions, etc., as is wellknown in the art.

[0089] Typically, hydrogen peroxide, or its addition compounds withurea, melamine, sodium borate or sodium carbonate, can be used in theform of a 3 to 12 percent, preferably 6 percent, aqueous solution as theoxidizing agent for developing the hair dye. Oxygen can also be used asthe oxidizing agent. If a 6 percent hydrogen peroxide solution is usedas oxidizing agent, the weight ratio of hair coloring composition anddeveloper composition is 5:1 to 1:5, but preferably 1:1. In general, thehair dyeing composition comprising primary intermediate(s) andcoupler(s), including at least one of the compounds of formula (1), isprepared and then, at the time of use, the oxidizing agents, such asH₂O₂, contained in a developer composition is admixed therewith until anessentially homogenous composition is obtained, which is applied shortlyafter preparation to the hair to be dyed and permitted to remain incontact with the hair for a dyeing effective amount of time. The mixtureof the oxidizing agent and the dye composition of the invention (i.e.,the hair dye product composition) is allowed to act on the hair forabout 2 to about 60 minutes, preferably about 15 to 45, especially about30 minutes, at about 15 to 5° C., the hair is rinsed with water, anddried. If necessary, it is washed with a shampoo and rinsed, e.g., withwater or a weakly acidic solution, such as a citric acid or tartaricacid solution. Subsequently the hair is dried. Optionally, a separateconditioning product may also be provided.

DYEING EXAMPLE 1

[0090] The following composition shown in Table 1 can be used for dyeingPiedmont hair. 100 g of the dyeing composition is mixed with 100 g 20volume hydrogen peroxide. The resulting mixture is applied to the hairand permitted to remain in contact with the hair for 30 minutes. Thedyed hair is then shampooed and rinsed with water and dried. The rangesof ingredients set out in Table 1 are illustrative of usefulconcentrations of the recited materials in a hair dye product. TABLE 1Composition for Dyeing Hair Ingredients Range (wt %) Weight (%)Cocamidopropyl betaine  0-25 17.00 Polyquaternium-22 0-7 5.00Monoethanolamine¹  0-15 2.00 Oleic Acid  2-22 0.75 Citric Acid 0-3 0.1028% Ammonium hydroxide¹  0-15 5.00 Behentrimonium chloride 1-5 0.50Sodium sulfite 0-1 0.10 EDTA 0-1 0.10 Erythorbic acid 0-1 0.40Ethoxydiglycol  1-10 3.50 C11-15 Pareth-9 (Tergitol 15-S-9) 0.5-5   1.00C12-15 Pareth-3 (Neodol 25-3) 0.25-5   0.50 Isopropanol  2-10 4.00Propylene glycol  1-12 2.00 p-phenylenediamine 0-5 1 mmole N,N-Bis(hydroxyethyl)-p-phenylene 0-5 1 mmole  diamine3-Methyl-p-aminophenol 0-5 1 mmole  p-Aminophenol 0-5 1 mmole  PrimaryIntermediate of this invention 0.5-5   4 mmoles 5-Amino-2-Methyl Phenol²0-5 3 mmoles 2,4-Diaminophenoxyethanol² 0-5 3 mmoles M-Phenylenediamine²0-5 1 mmole  Water qs to 100.00 qs to 100.00

[0091] Exemplary combinations of hair coloring components employing a4-amino-2-(1-aryloxy-ethyl)phenol compound of formula (1) of thisinvention are shown in Table 1 and in combinations C1 to C136 in TablesA through H. Reading down the columns, e.g., Table A, the Xesdemonstrate combinations of dyes that can be formulated according to thepresent invention. For example, in Combination No. C1 in Column 4 ofTable A, a primary intermediate compound of formula (1) of thisinvention (Row I of Table A), where R, Ar and y are as defined before,can be combined with 2-amino-phenol.

[0092] Especially preferred as the primary intermediate compounds offormula (1) in such combinations of Table I and Tables A through H arethe following:

[0093] 4-amino-2-(1-phenoxy-ethyl)-phenol

[0094] 4-amino2-[1-(4-amino-3-methyl-phenoxy)-ethyl]-phenol;

[0095] 4-amino-2-[1-(pyridin-3-yloxy)-ethyl]-phenol;

[0096] 4-amino-2-[1-thien-2-yloxy)-ethyl]-phenol;

[0097] 4-amino-2-[1-(furan-2-yloxy)-ethyl]-phenol;

[0098] 4-amino-2-[1-(4-amino-phenoxy)-ethyl]-phenol;

[0099]4-amino-2-{1-(2,3-dihydro-benzo[1,4]dioxin-6-yloxy)-ethyl}-phenol;

[0100] 4-amino-2-[1-(5-bromo-furan-2-yloxy)-ethyl]-phenol;

[0101] 4-amino-2-[1-(4-chloromethyl-phenoxy)-ethyl]-phenol;

[0102] 4-amino-2-[1-(4- methoxy-phenoxy)-ethyl]-phenol; and

[0103] 4-amino-2-{1-(benzo[1,3]dioxin-5-yloxy)-ethyl}-phenol. TABLE ADye Combinations Structure IUPAC Name Name C1 C2 C3 C4 C5 C6 C7 C8 C9C10 C11

X X X X X X X X X X X

2-Methyl-benzene-1,4- diamine p-Toluene-diamine

Benzene-1,4-diamine p-Phenylene-diamine

2-[(4-Amino-phenyl)-(2- hydroxy-ethyl)-amino]- ethanolN,N-Bis(2-hydroxy- ethyl)-p-phenylene- diamine

1-(2,5-Diamino-phenyl)- ethanol 1-Hydroxyethyl-p- phenylenediamine

4-Amino-3-methyl- phenol 3-Methyl-p- aminophenol

2-Amino-phenol o-Aminophenol X X

Benzene-1,3-diol Resorcinol X X X

2-Methyl-benzene-1,3- diol 2-Methyl-resorcinol X X

Naphthalen-1-ol 1-Naphthol X

2-Methyl-naphthalen-1- ol 2-Methyl-1-naphthol X

2-(2,4-Diamino- phenoxy)-ethanol 2,4-Diamino- phenoxyethanol X

Benzene-1,3-diamine m-Phenylenediamine X

3-Amino-phenol m-Aminophenol X

5-Amino-2-methyl- phenol 2-Hydroxy-4- aminotoluene X

2-(4,5-Diamino-pyrazol- 1-yl)-ethanol 1-Hydroxyethyl-4,5-diamino-pyrazole

[0104] TABLE B Dye Combinations Structure C12 C13 C14 C15 C16 C17 C18C19 C20

X X X X X X X X X

X X X

X

X X X X X X X

X

X

X

X

X

X

X

Structure C21 C22 C23 C24 C25 C26 C27 C28 C29

X X X X X X X X X

X X X X X X X X X

X

X X X

X

X X

X

X

X

X

X

[0105] TABLE C Dye Combinations Structure C30 C31 C32 C33 C34 C35 C36C37 C38

X X X X X X X X X

X X X X X

X X X X

X

X X X X X X

X

X

X

X

X

X

X

Structure C39 C40 C41 C42 C43 C44 C45 C46 C47

X X X X X X X X X

X X X X X X X X X

X

X X X X

X

X

X X

X

X

X

X

[0106] TABLE D Dye Combinations Structure C48 C49 C50 C51 C52 C53 C54C55 C56

X X X X X X X X X

X X X X

X X X X X

X

X X X X X

X

X

X

X

X

X

X

Structure C57 C58 C59 C60 C61 C62 C63 C64 C65

X X X X X X X X X

X X X X X X X X X

X

X X X X X

X

X

X

X X

X

X

X

[0107] TABLE E Dye Combinations Structure C66 C67 C68 C69 C70 C71 C72C73 C74

X X X X X X X X X

X X X X X X

X X X

X

X X X X

X

X

X

X

X

X

X

X X X X X X Structure C75 C76 C77 C78 C79 C80 C81 C82 C83

X X X X X X X X X

X X X

X

X X X X X X

X

X

X

X

X X

X

X

X X X X X X X X X

[0108] TABLE F Dye Combinations Structure C84 C85 C86 C87 C88 C89 C90C91 C92

X X X X X X X X X

X X X X X X X

X

X X X

X

X

X

X

X

X

X

X X X X X X X X X Structure C93 C94 C95 C96 C97 C98 C99 C100 C101

X X X X X X X X X

X X

X X X X X X X

X

X

X

X

X

X

X

X

X

X X X X X X X X X

[0109] TABLE G Dye Combinations Structure C102 C103 C104 C105 C106 C107C108 C109 C110

X X X X X X X X X

X X

X X X X X X X

X

X

X

X

X

X

X

X

X

X X X X X X X x x Structure C111 C112 C113 C114 C115 C116 C117 C118 C119

X X X X X X X X X

X X X X X X X

X X

X

X X X X X X X

X

X

X

X

X

X X

X

x x x x x x x x x

[0110] TABLE H Dye Combinations Structure C120 C121 C122 C123 C124 C125C126 C127 C128

X X X X X X X X X

X

X X X X X X X X

X

X X X X X X X X X

X

X

X

X

X

X

X X

x x x x x x x x x Structure C129 C130 C131 C132 C133 C134 C135 C136

X X X X X X X X

X X X X X X X X

X

X X X X X X X X

X

X

X

X

X

X

X

x x x x x x x x

[0111] With the foregoing description of the invention, those skilled inthe art will appreciate that modifications may be made to the inventionwithout departing from the spirit thereof. Therefore, it is not intendedthat the scope of the invention be limited to the specific embodimentsillustrated and described.

We claim:
 1. A compound of formula (1):

wherein R is selected from the group consisting of hydrogen, hydroxy,nitro, amino, halogen, C₁ to C₅ alkyl or haloalkyl, C₁ to C₅ alkoxy orcyclic alkoxy, C₁ to C₅ hydroxyalkyl and C₁ to C₅ hydroxyalkoxy; Ar isan aromatic group; and y=1 to
 3. 2. A compound of claim 1 wherein R ishydrogen, amino or C₁ to C₃ alkyl, and Ar is phenyl, pyridinyl, furanyl,2- or 3-thienyl, 2,3-dihydro-benzo[1,4]dioxin-5 or -6-yl orbenzo[1,3]dioxol-4 or -5-yl.
 3. A compound of claim 2 wherein Ar isphenyl.
 4. A compound of claim 2 wherein Ar is pyridinyl.
 5. A compoundof claim 2 wherein Ar is furanyl.
 6. A compound of claim 2 wherein Ar is2- or 3-thienyl.
 7. A process for the preparation of a compound offormula (1) of claim 1 comprising (a) subjecting a compound of formula(2) to hydrolysis

 to produce a compound of formula (3)

(b) protecting the hydroxy and amino groups of the formula (3) compoundby treatment thereof with di-tert-butyl dicarbonate to produce acompound of formula (4)

(c) reducing the compound of formula (4) with a reducing agent toprovide a compound of formula (5)

(d) subjecting the compound of formula (5) to the Mitsunobu reactionwith a reagent of the formula HO-Ar-(R)y to produce a compound offormula (6)

(e) and deprotecting the compound of formula (6) to produce a compoundof formula (1)

 wherein R, Ar and y are as defined in claim
 1. 8. A process accordingto claim 7 wherein R is selected from the group consisting of hydrogen,hydroxy, nitro, amino, halogen, C₁ to C₅ alkyl or haloalkyl, C₁ to C₅alkoxy or cyclic alkoxy, C₁ to C₅ hydroxyalkyl and C₁ to C₅hydroxyalkoxy; Ar is an aromatic group; and y=1 to
 3. 9. A processaccording to claim 7 wherein Ar is phenyl.
 10. A process according toclaim 7 wherein Ar is pyridinyl.
 11. A hair dye product comprising ahair dyeing composition containing at least one primary intermediate andat least one coupler and a developer composition containing one or moreoxidizing agents, the hair dyeing composition containing a primaryintermediate of formula (1):

wherein R is selected from the group consisting of hydrogen, hydroxy,nitro, amino, halogen, C₁ to C₅ alkyl or haloalkyl, C₁ to C₅ alkoxy orcyclic alkoxy, C₁ to C₅ hydroxyalkyl and C₁ to C₅ hydroxyalkoxy; Ar isan aromatic group; and y=1 to
 3. 12. A hair dye product according toclaim 11 wherein the hair dyeing composition additionally comprises aprimary intermediate selected from the group consisting of:2-methyl-benzene-1,4-diamine, benzene-1,4-diamine,2-(2,5-diamino-phenyl)-ethanol, 1-(2,5-diamino-phenyl)-ethanol,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, 4-amino-phenol,4-methylamino-phenol, 4-amino-3-methyl-phenol,1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol, 2-amino-phenol,2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol,N-(4-amino-3-hydroxy-phenyl)-acetamide, pyrimidine-2,4,5,6-tetramine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol, 1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine, and 1-(benzyl)-1H-pyrazole-4,5-diamine.13. A hair dye product according to claim 11 wherein the coupler presentin the hair dyeing composition is selected from the group consisting of:benzene-1,3-diol, 4-chlorobenzene-1,3-diol, naphthalen-1-ol,2-methyl-naphthalen-1-ol, 2-methyl-benzene-1,3-diol,2-(2,4-diamino-phenoxy)-ethanol,2-(3-amino-4-methoxy-phenylamino)-ethanol,2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and3-(2,4-diamino-phenoxy)-propan-1-ol, 3-amino-phenol,5-amino-2-methyl-phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol,3-amino-2-methyl-phenol, 3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1H-indol-6-ol, and2-aminopyridin-3-ol.
 14. A hair dye product according to claim 13wherein the hair dyeing composition additionally comprises a primaryintermediate selected from the group consisting of:2-methyl-benzene-1,4-diamine, benzene-1,4-diamine,2-(2,5-diamino-phenyl)-ethanol, 1-(2,5-diamino-phenyl)-ethanol,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, 4-amino-phenol,4-methylamino-phenol, 4-amino-3-methyl-phenol,1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol, 2-amino-phenol,2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol,N-(4-amino-3-hydroxy-phenyl)-acetamide, pyrimidine-2,4,5,6-tetramine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol, 1-(4-methyl benzyl)-1H-pyrazole-4,5-diamine, and 1-(benzyl)-1H-pyrazole-4,5-diamine.
 15. Ahair dye product according to claim 11 wherein Ar is phenyl.
 16. In ahair dyeing system wherein at least one primary intermediate is reactedwith at least one coupler in the presence of an oxidizing agent toproduce an oxidative hair dye, the improvement wherein the at least oneprimary intermediate comprises a compound of the formula (1):

wherein R is selected from the group consisting of hydrogen, hydroxy,nitro, amino, halogen, C₁ to C₅ alkyl or haloalkyl, C₁ to C₅ alkoxy orcyclic alkoxy, C₁ to C₅ hydroxyalkyl and C₁ to C₅ hydroxyalkoxy; Ar isan aromatic group; and y=1 to
 3. 17. A system according to claim 16wherein Ar is phenyl.
 18. A hair dyeing composition comprising, in asuitable carrier or vehicle, an effective hair dyeing amount of: (a) atleast one coupler, and (b) at least one primary intermediate comprisinga compound of the formula (1):

wherein R is selected from the group consisting of hydrogen, hydroxy,nitro, amino, halogen, C₁ to C₅ alkyl or haloalkyl, C₁ to C₅ alkoxy orcyclic alkoxy, C₁ to C₅ hydroxyalkyl and C₁ to C₅ hydroxyalkoxy; Ar isan aromatic group; and y=1 to
 3. 19. A hair dyeing composition of claim18 wherein Ar is phenyl.
 20. A hair dyeing composition according toclaim 18 additionally comprising a primary intermediate selected fromthe group consisting of: 2-methyl-benzene-1,4-diamine,benzene-1,4-diamine, 2-(2,5-diamino-phenyl)-ethanol,1-(2,5-diamino-phenyl)-ethanol,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, 4-amino-phenol,4-methylamino-phenol, 4-amino-3-methyl-phenol,1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol, 2-amino-phenol,2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol,N-(4-amino-3-hydroxy-phenyl)-acetamide, pyrimidine-2,4,5,6-tetramine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine, and1-(benzyl)-1H-pyrazole-4,5-diamine.
 21. A hair dyeing compositionaccording to claim 20 wherein the at least one coupler is selected fromthe group consisting of: benzene-1,3-diol, 4-chlorobenzene-1,3-diol,naphthalen-1-ol, 2-methyl-naphthalen-1-ol, 2-methyl-benzene-1,3- diol,2-(2,4-diamino- phenoxy)-ethanol,2-(3-amino-4-methoxy-phenylamino)-ethanol,2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and3-(2,4-diamino-phenoxy)-propan-1-ol, 3-amino-phenol,5-amino-2-methyl-phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol,3-amino-2-methyl-phenol, 3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1H-indol-6-ol, and2-aminopyridin-3-ol.
 22. A hair dyeing composition according to claim 18wherein at least one coupler is selected from the group consisting of:benzene-1,3-diol, 4-chlorobenzene-1,3-diol, naphthalen-1-ol,2-methyl-naphthalen-1-ol, 2-methyl-benzene-1,3-diol,2-(2,4-diamino-phenoxy)-ethanol,2-(3-amino-4-methoxy-phenylamino)-ethanol,2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and3-(2,4-diamino-phenoxy)-propan-1-ol, 3-amino-phenol,5-amino-2-methyl-phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol,3-amino-2-methyl-phenol, 3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1H-indol-6-ol, and2-aminopyridin-3-ol.
 23. A process for dyeing hair comprising forming ahair dye product composition by mixing a developer composition and ahair dyeing composition as defined in claim 18, applying to the hair anamount of the hair dye product composition effective to dye the hair,permitting the hair dye product composition to contact the hair forperiod of time effective to dye the hair, and removing the hair dyeproduct composition from the hair.
 24. A process according to claim 23wherein Ar is phenyl.